Methine dyes containing an isoindolobenzimidazolium or a benzopyrroloperimidinium nucleus



United States Patent Ofice 3,531 ,478 Patented Sept. 29, 1970 3,531,478METHINE DYES CONTAINING AN ISOINDOLO- BENZIMIDAZOLIUM OR A BENZOPYRROLO-PERIMIDINIUM NUCLEUS Gather Irick, Jr., Kingsport, Tenn., assignor toEastman Kodak Company, Rochester, N.Y., a corporation of New Jersey NoDrawing. Filed May 29, 1967, Ser. No. 642,238 Int. Cl. C09b 23/04, 23/10US. Cl. 260-240 13 Claims ABSTRACT OF THE DISCLOSUREIsoindolobenzimidazolium, benzopyrroloperimidinium compounds and methinedyes derived therefrom having utility as dyes for synthetic materialsand as intermediates in the preparation thereof.

respectively, by the general Formulae I and II, below,

while the novel methine compounds and cations are characterized by thegeneral Formulae Ill and 1V, below:

HCX

wherein R represents an alkyl group or an aralkyl group;

R R and R are the same or different and each represents hydrogen, analkyl group or an alkoxy group; and X represents an aldehyde residue.

The cations represented by Formulae I and II are useful, as will be morefully explained hereinafter, for the preparation of the methine cationsrepresented by Formulae III and IV. The methine cations of the inventionare useful, as will similarly be more fully explained hereinafter, fordyeing acrylic and modacrylic fibers, yarns and fabrics colors whichrange from bright shades of orange to deep shades of blue. Illustrativetextile materials which can be dyed with the methine cations includeacrylic, modacrylic, acid-modified acrylic and sulfonate-rnodifiedpolyester materials.

Typical of the alkyl groups represented by R are the lower alkyl groupsof up to about 4 carbon atoms such as methyl, ethyl, n-propyl andn-butyl. A typical aralkyl group represented by R is the benzyl group.

Representative alkyl groups and alkoxy groups represented by R R and Rare the lower alkyl groups having up to about 4 carbon atoms, such asmethyl. ethyl, npropyl, n-butyl and the lower alkoxy groups such asmethoxy, ethoxy, etc.

The aldehyde residues represented by X are characterized by the formulaeR5 @MQ R n R wherein R represents lower alkyl, each R representshydrogen or lower alkyl and R", R and R are the same or different andeach represents hydrogen, a lower alkyl group, e.g. methyl, ethyl,n-propyl or a substituted alkyl group such as an alkoxyalkyl group, e.g.Z-methoxyethyl, a cyanoalkyl group, e.g. 2-cyanoethyl, a carboxylic acidimidoalkyl group, e.g. 2-succinimidoethyl or a haloalkyl group, e.g.2-chloroethyl, Z-brornoethyl. etc.

R and R are the same or diflerent and each represents hydrogen, a loweralkyl group, e.g. methyl, ethyl, an alkoxy group, e.g. methoxy, ethoxy,or halogen, e.g. bromo, chloro. Where R or R represent substituents suchas hydrogen or a lower alkyl group, such substituents can be the same ordifferent than the corresponding substituents constituting R, R and R.

In a particularly preferred group of the novel compounds of theinvention represented by general Formulae I, II, III and IV, Rrepresents methyl, R R and R represent hydrogen and X representsaldehyde residues, as described above, wherein R represents methyl, eachR represents hydrogen or methyl, R R and R are the same or different andeach represents hydrogen, methyl, ethyl or cyanoethyl and R and Rrepresent hydrogen, methyl, methoxy, ethoxy, or chloro.

The novel cations of the invention are prepared, in the case of thecations of Formula I by the reaction of phthalide or an appropriatelysubstituted derivative thereof with o-phenylenediamine hydrochloride oran appropriately substituted derivative thereof to give isoindolo(2,1-a)benzimidazolium chloride and treatment of such salt with a baseto give the isoindolobenzimidazole which is unsubstituted in the5-position as described by Bistrzycki et al., Annalen 415, 1 (I917).Quaternization of the unsubstituted isoindolobenzirnidazole with asuitable quaternizing agent, such as an alkyl halide, e.g. methyliodide, an aralkyl halide, e.g. benzyl chloride, or a dialkyl sulfate,e.g. dimethyl sulfate, etc., produces the novel S- substituted compoundsof Formula I.

In the case of the cations of Formula II, the benzo(3,4)pyrrolo(l.2-a)perimidine which is unsubstituted in the 5- position isprepared, as described above by Bistrzyclti et 111.. by the reaction ofan appropriate phthalide and an appropriate 1,8-naphthalenediaminehydrochloride to give a benzo(3,4)pyrrolo(1,2-a)perimidiniumhydrochloride. Subsequent treatment thereof with base yields thebenzopyrroloperimidine which is unsubstituted in the 7position.Quaternization as set forth above, gives the novel 7substituted cationsof Formula II.

Upon condensation of the novel cations of Formulae I and II with anappropriate aldehyde, in the presence of acetic anhydride, the novelmethine cations of Formulae III and IV are obtained.

The aldehyde compounds which are condensed with the cations of FormulaeI and II to obtain the methine compounds and methine cations of FormulaeIII and IV are commercially available and/or are prepared by well knownprocedures. Thus, the aldehydes are selected from the following types:

Type A Type 13 in RE A I one N Q Q t.

tt) Rtt [0 R Type 1*] /ll OIIU-HU:11C 1:)

a lill) It has thus been found that reaction of the unsubstitutedisoindolobenzimidazole and benzopyrroloperimidine compounds withquaternizing agents will produce the previously unknown quaternaryfi-substituted isoindolog5 benzimidazolium and 7-substitutedbenzopyrroloperimidinium cations of the invention. Further, it has beenfound that the quaternary nitrogen atom activates the methylene group inthe ll-position of the compounds of Formula I and the correspondingmethylene group in the 12-position 30 of the cations of Formula IIwhereby such will readily condense with the above-described aldehydes toyield the novel methine cations represented by Formulae II and IV.

The following series of reactions illustrates a convenient mode ofpreparing the cations of the invention.

R IICI N R K) 1h lbuse l quaternization R Ill 63 R x) (ll) It X-G IIOacetic auhydride (IV) C-X In addition to o-phenylenediamine (i.e.1,2-diaminobenzene), the following substituted derivatives thereof areused to prepare the novel cations of Formulae I and III of theinvention: 3-methyl-1,Z-diaminobenzene, 4- methyl-1,2-diaminobenzene, 3ethyl 1,2 diaminobenzene, 4 ethyl 1,2 diaminobenzene,3-n-propyl-l,2-diaminobenzene, 4-n-propy1 1,2 diaminobenzene, 3-nbutyl1,2 diaminobenzene, 4-n-butyl 1,2 diaminobenzene, 3 methoxy 1,2diaminobenzene, 4-methoxy- 1,2 diaminobenzene, 3 ethoxy 1,2diaminobenzene, 4 ethoxy 1,2 diaminobenzene, etc. Particularly preferredare 1,2-diaminobenzene and those derivatives thereof containing a methylgroup in positions 3 or 4.

The phthalide reactants utilized in preparing the cations of Formulae I,II, III, and IV of the invention include phthalide (i.e. l-phthalanone)and the following substituted derivatives thereof:3-methyl-1-phthalanone, 4- methyl-l-phthalanone, 5-methyl-1-phthalanone,6-methyll-phthalanone, 3-ethyl-1-phthalanone, 4-ethyl-l-phathalanone, Sethyl 1 phthalanone, 6-ethyl-1-phthalanone,

3-n-propyl-l-phthalanone, 4-n-propyl 1 phthalanone, 5 npropyl-l-phthalanone, 6-n-propyl-1-phthalanone, 3n-butyl 1 phthalanone,4-n-butyl-l-phthalanonc, S-nbutyl 1 phthalanone, 6-nbutyl-lphthalan0ne,3-methoxy-l-phthalanone, 4-methoxy-lphthalanone, S-methoxyl-phthalanone,6-meth0xy-l-phthalanone, 3-ethoxy 1- phthalanone, 4 ethoxy 1phthalanone, 5 ethoxy 1- phthalanone, 6 ethoxy 1 phthalanone, etc.Preferred compounds are 1 phthalunone and derivatives thereof containinga methyl group in positions 3, 4, 5 or 6.

In addition to 1,8-naphthalenediamine, the following derivatives thereofare utilized in preparing the cations of Formulae II and IV: 2,7dimethyl-l,S-naphthalenediamine, 3 methyl-1,8 naphthalenediamine,3,6-dimethyl- 1,8 naphthalenediamine, 5 methyl 1,8-naphthalenecliamine,4,5 dimethyl 1,8 naphthalenediamine, 2,7- diethyl 1,8naphthalenediamine, 3 ethyl-1,8-naphthalenediamine, 3,6 diethyl 1,8naphthalenediamine, 5- ethyl 1,8 naphthalenediamine, 4,5 diethyl 1,8-naphthalenediamine, 2,7 di n propyl 1,8 naphthalenediamine, 3,6 di npropyl-l,S-naphthalenediamine, 4-n-propyl-1,8-naphthalenediamine, 4,5 din propyl- 1,8 naphthalenediamine, 6-n-propyl 1,8 naphthalenediamine, 2,7di n butyl 1,8-naphthalenediamine, 3- n-butyl-l,8-naphthalenedian1ine,3,6 di-n-butyl 1,8- naphthaleneeliamine, 6-n-butyl1,8-naphthalenediamine, 4,5 di n-butyl-1,8-naphthalenediamine,2,7-dimethoxy- 1,8 naphthalenediamine, 3,6 dimethoxy1,8-naphthalenediamine, 4 methoxy 1,8 naphthalen ediarnine, 4,5-dimethoxy 1,8 naphthalenediamine, 6 methoxy 1,8- naphthalenediamine, 2,7diethoxy 1,8 naphthalenediamine, 3 ethoxy 1,8 naphthalenediamine, 3,6diethoxy 1,8 naphthalenediamine, 5-ethoxy-1,8-naphthaenediamine, etc.Preferred compounds include 1,8-naphlenediamine, 4,S-diethoxy-1,8-naphthalenediamine, etc. 4

Preferred compounds include 1,8 naphthalenediamine and derivativesthereof containing at least one methyl group in positions 2, 3 or 4.

Representative isoindolobenzimidazoles and benzopyr. roloperimidineswhich are utilized in accordance with the invention areS-methylisoindolotZ,1-a)benzimidazole, 5-ethylisoindolo(2, 1-a)benzirnidazole, 5 benzylbenzoisoindolo(2, 1 -a)benzimidazole,

3 ,5 -dimethylisoindolo(2, 1 -a)benzimidazole,

5 ,8-dimethylisoindolo(2, 1-a)benzimidazole,

3 -n-butyl-5-methylisoindolo(2,1-a)benzimidazole, 2,5,8-trirnethylisoindolo(2, l-a)benzimidazole,2-n-propyl-5,8-dimethylisoindolo(2,1-a)benzimidazole,3-methoxy-S-methylisoindolotZ,1-a)benzimidazole,7-ethoxy-3,5-dimethylisoindolo(2,l-a)benzirnidazole,3-methyl-5-ethylisoindolo(2,1-a)benzimidazole,8-n-propyl-5-methylisoindolo(2, l-a)benzimidazole,2,8-dimethyl-5-benzylisoindolo(2,1-a)benzimidazole,

7-n-butyl-5-methylisoindolo(2,l-albenzimidazole,7-methylbenzo(3,4)pyrrolo(1,2-a)perimidine,3,7,9-trimethylbenzo(3,4)pyrrolo(1,2-a)perimidine,2,4,7,10-tetramethylbenzo(3,4)pyrrolo(1,2-a)perimidine,7,9-dimetl1ylbenzo(3,4)pyrrolo(1,2-a)perimidine,2,7dimethyl-l1-methoxybenzo(3,4)pyrrolo(l,Z-a)

perimidine, 2.5-dimethyl-7-benzylbenzo(3,4)pyrrolo(1,2-a)perimidine,

etc.

Preferred compounds are 5-methylisoindolo(2, 1-a)benzirnidazole and7-methylbenzo(3,4)pyrrolo(l ,2-a)perimidine.

Representative aldehydes utilized in accordance with the inventioninclude 1,3,3-trimethyl-2-methylene-omega-formylindoline,1-chloroethyl-3 ,3-dimethyl-2-methylene-omega-formylindoline, 1,3,3-triethyl-2-methylene-omega-formylindoline,1-cyanoethyl-3,3-dimethyl-2-methylene-omega-formylindoline,1-methyl-3,3-diethyl-2-methylene-omega-formylindoline,4-(N-ethyl-N-fi-cyanoethyl)-2-rnethylbenzaldehyde, 4-(N-ethyl-N-8-methoxyethyl)-Z-methylbenzaldehyde,4-(N-cyanoethyl-N-p-chloroethyl)-2-methylhenzaldehyde,4-(N-cyanoethyl-N-fl-ethyl)-2-methylbenzaldehyde,4-(N,N-dichloroethyl)-2-methylbenzaldehyde,4-(N-chloroethyl-N-fi-ethyD-Z-methylbenzaldehyde, 4-(NpropyI-N-p-cyanQethyD-Z-methylbenzaldehyde,4-[N-ethyl-N-fl-succinimidoethyD-Z-methylbenzaldehyde,N-methyl-4'-ethoxy-4-formyldiphenylamine,N-chloroethyl-4-formyldiphenylamine, N-methyl-4-formyldiphenylamine,N-ethyl-4'-methoxy-4-formyldiphenylamine,N-cyanoethyl-4'-ethoxy-4-formyldiphenylamine,N-ethyl-4'-ethoxy-4-formyldiphenylamine,2,7-dimethyl-N-cyanoethyl-fi-formyl-1,2,3,4-tetrahydroquinoline,2,7-dimethyl-N-ethyl-G-formyl-1,2,3,4-tetrahydroquinoline,2-rnethyl-7-ethyl-N-cyanoethyl-6-formyl-1,2,3,4-tetrahydroquinoline,2-methyl-7-ethyl-N-chloroethyl-6-formyl-1,2,3,4-

tetrahydroquinoline, p-dimethylaminocinnamaldehyde,p-(N-ethyl-N-;8-chloroethyl)aminocinnamaldehyde,p-(N-ethyl-N-fl-cyanoethyDaminocinnamaldehyde,p-(N-chloroethyl-N-B-cyanoethyDaminocinnamaldehyde,o-methyl-p-(N-cyanoethyl-N-fl-ethybaminocinnamaldehyde, etc.

The novel methine cations of the invention, of course, exist incombination with an anion such as, for example, Ci Br, I-, CH Q4", C HSO etc., the anion dependmg on the method of preparation utilized andthe particular quaternizing agent employed. The anion does not affectthe utility of the methine cations of the invention as dyes nor does itailect the dye afiinity of the cations for polyacrylonitrile textilematerials. When the compounds are used to dye polyacrylonitrile textilematerial, the amon becomes associated with a positively charged ionderived from the polyacrylonitrile and is removed from the dye cationand polyacrylonitrile textile material, either in the dyebath or in asubsequent washing of the dyed polyacrylonitrile textile material. Sincethe cation of a cationic methine dye is responsible for the color of thecompound and the particular anion associated with the cation is notimportant, the novel methine cations of the invention are describedherein without being associated with an anion.

Suitable quaternizing agents which can be used in preparing the novelmethine cations of the invention are the dialkyl sulfates, the alkylhalides, the aralkyl halides, the alkyl esters of sulfonic acids, etc.Specific quaternizing agents include, for example, dimethyl sulfate,diethyl sulfate, dipropyl sulfate, dibutyl sulfate, ethyl bromide,methyl iodide, ethyl iodide, n-butyl iodide, benzyl chloride, benzylbromide, methyl-p-toluene sulfonate, butyl-ptoluene sulfonate and ethylbenzene sulfonate.

The following examples will serve to further describe and illustrate theinvention.

EXAMPLE 1 Isoindolo(2,l-a)benzimidoazolium chloride A mixture of 23 g.o-phenylene diamine, 23 m]. concentrated hydrochloric acid and 100 ml.of methanol is stirred for minutes and evaporated to dryness to giveo-phenylenediamine hydrochloride which is then mixed with 28.6 g. ofphthalide and heated to 200". After 45 minutes the mixture is cooled,slurried in cold water and filtered to giveisoindolo(2,l-a)benzimidazolium chloride.

EXAMPLE 2 Isoindolo(2, 1-a)benzimidazole The hydrochloride salt fromExample 1 is suspended in 800 ml. of water and made basic by addition ofammonium hydroxide. Filtration and water washing gives the crudeproduct. Recrystallization from ethanol and from toluene gives thenearly colorless crystalline isoindolo- (2,l-a)benzimidazole. It has thestructure:

EXAMPLE 3 A solution of 3.09 g. isoindolo(2,l-a)benzimidazole, 2.50 g.methyl iodide and 100 ml. of ethanol is refluxed for 5 hours on a steambath. Cooling to C. precipitates the product which is isolated byfiltration. Recrystallization from water gives the analytically pureS-methylisoindolotZ.l-a]benzimidazolium iodide which melts withevolution of gas at 250-300". It has the structure:

(ills In accordance with the above procedure, the S-substitutedisoindolo(2,l-a)benzimidazoles of Table I are prepared:

TABLE I R R R H II I I 3-nietl1oxy II II II 3incthyl ti-mcthyl II 8ntulhyl 3-1ncthyl II B-nwthyl Sanethyl lqnethyl Tat-propy] II (tn-DutylII St-methy] 2-n-propyl II 3ubutyl S-cthoxy .5 methyl EXAMPLE 1'! Amixture of 6.2 g. isoindolo(2,l-a)benzimidazole and ml. of dimethylsulfate is heated to solution at reflux, cooled and held at 100 for /2hour, during which time crystallization occurs: The mixture is pouredinto 400 ml. of dry ether, filtered and the solids are ether washed anddried for a few minutes at room temperature. Solids are dissolved in 300ml. of water and a solution of 15 g. potassium bromide in ml. of wateris added. Filtration and drying gives 5methylisoindo]o[Z,l-a)benzimidazolium bromide, melting point 266-286".It has the structure:

C Ila EXAMPLE 18 In accordance with the above pnocedure, the cations inTable II are prepared from type A aldehydes and 5- substitutedisoindolo(2,l-a)benzimidazolium halides.

TABLE II Example N0. R R R R R ]I II methyl methyl ]1 3-uiethyl methylmethyl S-muthyl lI ethyl ethyl s-melhyl 4-mothyl ethyl ethyl EXAMPLE 23Preparation of methine cation by reaction of an aldehyde of type B withS-methylisoindolo(2,l-a)benzimidaz0- lium iodide A mixture of 0.52 g.S-methylisoindolo(2,l-a)benzimidazolium iodide, 0.33 g.4-(N-ethyl-N-B-cyanoethyl)-2- methylbenzaldehyde and 25 ml. aceticanhydride is refluxed for 45 minutes, cooled to 25 C. and diluted with50 ml. of diethyl ether. Solids are collected by filtration and washedwith 20% potassium iodide solution. Drying gives 0.3 g. of the cationwhich dyes modacrylic fibers an orange-red shade and has the structure:

69 fi e? In accordance with the above procedure, the cations in TableIII are prepared. The cations conform to Formula III in which Xrepresents a type B aldehyde.

TABLE III R] R2 R3 R7 R7 R8 RIO Example:

24 methyl H H ethyl 2Cl-ethyl Q-methyl S-methyl H ethyl 2CN-ethyl2-methyl yl H 3-rnethyl ethyl ZEN-ethyl ZmethyI 27 benzyl &methyl4-methyl 2-Cl-ethyl 2-CN-ethyl 3-methy1 TABLE V Example R R R R" R R9 HII methyl 2 methyl ethyl E-methyl H methyl Z-methyl Z-CN-ethyl H4-methyl ethyl 2-methyl 2-CN-ethyl S-methyl 3-rnethyl ethyl 2-mathyl2-Cl-ethyl 38 methyl H H methyl 2,2,4-trimethyl 2-Cl-ethyl EXAMPLE 28 rThe cations of Table V are prepared according to the n) Preparation ofmethine cation by reactlon of an aldehyde Procedure described Example oftype C with 5-methylisoind0l0(2,l-a)benzimidazo- EXAMPLE 39 hum md'dePreparation of methine cation by reaction of an aldehyde Amixture of0.52 g. 5-methylisodinolo(2,l-a)benzimidof type E with 5methylisoindole(2,1 a)benzimidazoliurn iodide, 0.38 g. N-rnethyl-4'-ethoXy-4-f0rmyldiazolium iodide phenylamine and ml. of acetic anhydrlde 1srefluxed A mixture of OJ 9 sdnmhylisoindolou,l a)benzimid for 45minutes, cooled to 25 C. and diluted with 50 ml. of diethyl ether.Filtration, ether washing and drying 211 23 3 13 83i iyg fi i zli zgzgat i? 5332:

gives of the dye which imparts a red Shade to cooled to 10 C. andfiltered. Solids are washed first with 2 modacr fibers and has theStructure 0 acetic acid, then with n-hexane and dried. 0.42 g. of theCH3 cation is obtained which dyes modacrylic fibers a violet I116) shadeand has the structure:

Q N N\ F C IIC IIII'IC l The cations 111 Table IV are prepared inaccordance Q l with the procedure described in Example 28 and conform Cmto Formula III in which X represents the residue of a The cations ofTable VI are prepared as described in type C aldehyde. Example 39.

TABLE VI R1 R2 R3 R1 Rs R10 Example.

40 methyl H H ethyl 2-Clethy1 2-methyl 41 methyl H H ethyl 2-Cl-ethyl2-nlethyl 42 ethyl H methyl ethyl 2-CN-ethyl 3-methyl 43 benzyl methyl H2-Clethyl 2-CN-ethyl 21nethyl TABLE IV EXAMPLE 44 E R1 R2 R3 R8 RIO RllB enzo34 rrl 2- 29 "methyl H H methyl H H o )py 00(1, a)perirn1d1n1umhydrochloride 30 methyl 8-metllyl II methyl 4-ethoxy II J I a1 ethyl H4-methyl ethyl ti-memoir} H A mixture of 15.8 g. ofl,8-r1aphthalened1am1ne, 11 ml. .12 benzyl Emethyl EHYlethYl emyl H ofconcentrated hydrochloric acid and 75 ml. ethanol is EXAMPLE 3 stirredfor 5 minutes and evaporated to dryness to give 1,8 -naphtha lenediaminehydrochloride. The 1,8-naphm d l 2,1 be 55 thalenedlamine hydrochlorideis mixed with 14.3 g. of

2252 53 2 :2? 5 me y lsom oo( n phthahde and the mixture is heated at205 C. for 15 A mixture of 0 52 g 5 methylisoindoloa 1 a)benz minutes.Upon cooling, the mixture is recrystallized from Preparation of methinecation by reaction of an aldehyde hydride is refluxed for 1 hour, cooledand diluted with EXAMPLE 45 75 ml. of ether. Filtration, washing withdilute potassium iodide solution and drying gives 0.3 g. of a cationwhich Benz0(3,4)pyrr010(LZamerimidiHe dyes modacrylic fibers red and hasthe structure:

CH: 65 The hydrochloride salt from Example 44 is dissolved in 600 ml. ofhot, aqueous ethanol and concentrated as N\ ammonium hydroxide is addeduntil the solution becomes basic. Filtration at 30 C. and drying give16.0 g. of the N olive-colored benzo(3,4)-pyrrolo(1,2-a)perimidine. Ithas Y the structure:

1 1 EXAMPLE 46 7-methyl-benzo 3,4 pyrrolo( 1,2-a perimidinium bromide Amixture of 5.12 g. of benzopyrroloperimidine and ml. dimethyl sulfate isheated at 150 C. for 0.5 hours, cooled and mixed with 200 ml. diethylether. The solids are separated, washed with ether, and dissolved in 300ml. of hot water. After filtration, a solution of 10 g. potassiumbromide in 40 ml. water is added. Filtration at C. and drying gives theorange solid, 7-methyl-benzo (3,4)pyrrolo(l,2-a)perimidinium bromide. Ithas the structure:

In accordance with the procedure described in Example 46, the7-substituted benzo(3,4)pyrrolo(1,2-a)perimid- I ines of Table VII areprepared.

TABLE v11 Z-methyl 2-methyl H 2 methyl B-methyl 3 methyl II IO-methyl4-methyl H H Q-methyl H methoxy 4-methyl H B-methyl S-methyl EXAMPLE 53Preparation of methine cation by reaction of an aldehyde of type A with7-methyl-benzo(3,4)pyrrolo(l,2-a)perimidinium bromide A mixture of 0.35g. 1,3,3 trimethyl 2 methyleneomega-formylidinoline, 0.53 g. 7methyl-benzo(3,4) pyrrolo(1,2-a)perimidinium bromide and 8 ml. of aceticanhydride is refluxed for 1 hour, cooled to 300 C., and mixed with 100ml. of diethyl ether. Solids are filtered off, ether washed and slurriedin 100 ml. of 2% potassium bromide. Filtration and drying gives a bluecation which dyes modacrylic fibers blue and has the structure:

The cations described in Table VIII are prepared in accordance with theprocedure of Example 53 and conform to Formula IV in which R, R and Rare hydrogen and X is the residue of a type A aldehyde.

TABLE VIII R R B Example:

5* methyl methyl Cl-ethyl 55 ethyl methyl CN-ethyl 56 ethyl methylmethyl 5? benzyl methyl methyl EXAMPLE 58 Preparation of methine cationby reaction of an aldehyde of type B with7-methyl-benzo(3,4)pyrrolo(l,2-a)perimidinium bromide A mixture of 0.53g. 7 methyl benzo(3,4)pyrrolo (1,2-a) perimidinium bromide, 0.38 g. 4-(Nethyl- N-fi-cyanoethyl) Z-methylbenzaldehyde and 8 ml. acetic anhydrideis refluxed for 2 hours, cooled to C., and

mixed with 300 ml. of ether. Solids are filtered, washed with ether, andslurried in 100 ml. of 2% potassium 1 2 bromide. Filtration, waterwashing, and drying gives 0.7 g. of a cation that dyes modacrylic fibersblue. It has the structure:

JJlIa The cations set forth in Table 9 are prepared as described inExample 57 and have the general Formula IV in which R R and R arehydrogen and X is the residue of a type B aldehyde.

TA B LE I X Ex. R R R It 2-Cl-ethyl. ethyl Z-methyl Mnethoxyethyl ethylZ-methyl 2-Cl-ethyl (ll-ethyl 3-mothyl 2-C N-ethyl ethyl 3-n1ethyl Z-C Ncthyl n-propyl H .Z-CN-ethyl ethyl Z-methyl 2-Br-etl1yl ethyl .Z-ruuthyl2 C Nethyl ethyl 2-methyl 2-Cl-ethyl ethyl 2-ethyl Z-CI-ethyl ethyl2-methy il-succlnimldoethyl ethyl Z-methy EXAMPLE 70 The cations in thefollowing table are prepared as described in Example 69 and conform toFormula IV wherein R R and R are hydrogen and X represents the residueof a type C aldehyde.

TABLE X B1 s Rlt) Rn Example:

71 methyl methyl H 2-methyl ethyl H 2-methyl 2- lethyl 4'-methoxy2-methyl 2-CNethyl 4methoxy 2methyl 2-Cl-ethyl H H methyl H 2-methylmethyl 4-methoxy II ethyl 4-methyl II EXAMPLE 79 Preparation of methinecation by reaction by type D aldehyde with 7 methyl benzo(3,4)pyrrolo(1,2-a) perimidinium bromide A mixture of 0.53 g.7-methyl-benzo(3,4)pyrrolo(1,2- a)perimidinium bromide, 0.36 g.2,7-dimethyl-N-cyanoethyl-fi-formyl l,2,3,4 tetrahydroquinoline and 10ml. acetic anhydride is refluxed for 1 hour, cooled to 25 C. and mixedwith 50 m1. of diethyl ether. Solids are filtered off, washed with etherand then washed with 10% aqueous potassium bromide. Water washing anddrying gives 13 0.6 g. of a cation which dyes modacrylic fibers violet.It has the structure:

H: Q-g

H/ H C HaC CH:

N hHaC N In accordance with the procedure of Example 78, the followingcations are prepared:

TABLE XI R1 R a R methyl 2-methyl ethyl methyl Z-methyl 2-(Jl-ethylmethyl 2-methyl ethyl methyl 2,2,4-trimethyl 2-CN-ethyl methyl2,2,4-tr1'methyl 2-Cl-ethyl methyl 2-methy1 2-CN-ethyl methyl Z-methylethyl methyl 2-methyl 2-Cl-ethyl EXAMPLE 88 The cations in the followingtable are prepared in accordance with the procedure described in Example87 and conform to general Formula IV in which R R and R are hydrogen andX represents a residue of a type E aldehyde.

TABLE XII R1 R1 Rs R10 methyl ethyl Z-CN-ethyl Z-methyl methyl ethyl 2-0N-ethyl 2-methyl methyl 2-Cl-ethyl 2-Cl-ethyl 2-methyl benzyl Z-CN-ethyl2-Cl-ethyl 2-methyl benzyl et 1 ethyl El-methyl benzyl Z-CN-ethyl ethylQ-methyl 95 methyl ethyl ethyl 2-ethyl The methine cations of theinvention can be used, as described above, for dyeing acrylic andmodacrylic polymer fibers, yarns and fabrics giving shapes of orange toblue when applied thereto by conventional dye methods. Acrylic textilematerials are those which consist of at least 85% acrylonitrile andmodacrylic textile materials are those consisting of at least but lessthan 85% acrylonitrile. The compounds of the invention also giveexcellent dyeings on acid-modified acrylic textile materials such as thesulfonate modified acrylic fibers described in US. Pats. 2,837,500,2,837,501 and 3,043,811. The novel compounds and cations can also beused to dye sulfonate modified polyester fibers such as are described inUS Pat. 3,018,272. Examples of the textile materials that are dyed withthe compounds and cations of the invention are those sold under thetrade names Orlon," Orlon 42, Verel, Acrilan, Dynel, Creslan and Dacron64.

Textile materials dyed by the cations of the invention are characterizedby containing at least about 35% combined acrylonitrile units and up toabout 95% acrylonitrile units, and modified, for example, by 65-5% ofvinyl pyridine units as described in US. Pats. 2,990,393 (Re. 25,533)and 3,014,008 (Re. 25,539) or modified by 655% of vinylpyrrolidoneunits, for example, as described by U.S. Pat. 2,970,783, or modifiedwith 65-5% acrylic ester or acrylamide units as described in US. Pats.2,879,253, 2,879,254 and 2,838,470. Similar amounts of the otherpolymeric modifiers mentioned above are also useful. A preferred groupof the copolymers readily dyeable with the dyes of the invention are themodacrylic polymers such as described in US. Pat. 2,831,826 composed ofa mixture of (A) 70-95% by weight of a copolymer of from 30 to 65% byweight of vinylidene chloride or vinyl chloride and 70-35% by weight ofacrylonitrile, and (B) 30-5 by weight of a second polymer from the groupconsisting of (1) homopolymers of acrylamidic monomers of the formula Rii Gib-:C-C-N wherein R is selected from the group consisting ofhydrogen and methyl, and R and R are selected from the group consistingof hydrogen and alkyl groups of 1-6 carbon atoms, (2) copolymersconsisting of at least two of said acrylamidic monomers, and (3)copolymers consisting of at least 50% by weight of at least one of saidacrylamidic monomers and not more than 50% by weight of a polymerizablemonovinyl pyridine monomer.

Another type of modacrylic polymer that can be dyed with the cations ofthe invention is an acetone soluble mixture of (A) 70-95% by weight of acopolymer of 30-65% by weight of vinylidene chloride and 70-35% byweight of acrylonitrile and (B) 30-5% by weight of an acrylamidehomopolymer having the above formula wherein R R R are as describedabove. Specific polymers of that type contains 70-95% by weight of (A) acopolymer of from 30-65% by weight of vinylidene chloride and 70-35% byweight of acrylonitrile and (B) 30-5% by weight of a lowerN-alkylacrlyamide polymer such as poly-N-methacrylamide,poly-N-isopropylacrylamide and poly-N-tertiarybutylacrylamide.

The following example illustrates one way in which the methine cationsof the invention can be used to dye acrylonitrile polymer textilematerial.

EXAMPLE 96 An amount of 0.1 gram of dye is dissolved by warming in 5 cc.of methyl Cellosolve. A 2% aqueous solution of a nonionic surfactant,such as Igepal CA (a polymerized ethylene oxide-alkylphenol condensationproduct), is added slowly until a fine emulsion is obtained and then thedye mixture is brought to a volume of 200 cc. with warm water. Five cc.of a 5% aqueous solution of formic acid or acetic acid are added andthen 10 grams of fabric made from an acrylic fiber is entered and, inthe case of Orlon 42 acrylic textile materials, the dyeing is carriedout at the boil for one hour. In the case of materials made of Verelmodacrylic fiber the dyebath temperature should not exceed C. in orderto avoid damage to the fiber. The dye material in then washed well withwater and dried.

15 The invention has been described in considerable detail withparticularly reference to certain preferred embodiments thereof, but itwill be understood that variations and modifications can be effectedwithin the spirit and scope of the invention as described hereinaboveand as defined in the appended claims.

Q represents an acid anion;

R represents a lower alkyl group or a benzyl group;

R R and R are the same or different and each represents hydrogen, analkyl group or an alkoxy group; and

X represents an aldehyde residue selected from the group consisting ofand R 1 N/ HC=IIC N/ RT a R10 R10 wherein R represents lower alkyl;

R represents hydrogen or lower alkyl',

R", R and R are the same or different and each represents hydrogen,lower alkyl, or lower alkyl substituted with lower alkoxy, cyano, lowercarboxylic acid imido, or halogen; and R and R are the same or differentand each represents hydrogen, lower alkyl, lower alkoxy or halogen. 2. Acation as defined in claim 1 wherein R represents methyl or benzyl; Rand R represent hydrogen, methyl or methoxy. 3. A compound as defined inclaim 1 having the formula wherein Q represents an acid anion.

4. A compound as defined in claim 1 having the formula wherein Qrepresents an acid anion.

5. A compound as defined in claim 1 having the formula wherein Qrepresents an acid anion.

6. A compound as defined in claim 1 having the formula mam HI G 1 Q N oll HC HIC CHI N II'IACN wherein Q represents an acid anion.

7. A compound as defined in claim 1 having the formula wherein Qrepresents an acid anion.

8. A compound as defined in claim 1 having the formula y (HI N G/ HIC-Ht' \N wherein Q represents an acid anion.

17 18 9. A compound as defined in claim 1 having the formula R: lg Q R:

It CH 1 l I, Q6 l, N \C, wherein HEQN Q represents an acid anion;

HWN m R represents a lower alkyl group or a benzyl group; mo '2 R -l-Rare the same or different and each represents hydrogen, an alkyl groupor an alkoxy group; and X represents an aldehyde residue selected fromthe wherein Q represents an acid anion.

group consisting of 1 0. A compound as defined in claim 1 having the N/IIG:IIC- -N/ wherein Q represents an acid anion. m

11. A compound as defined in claim 1 having the Rm Rm formula m N- CllaQ Q 9 1L6) Q Rll lilo Q wherein R represents lower alkyl;

\ R represents hydrogen or lower alkyl;

1L R", R and R are the same or different and each represents hydrogen,lower alkyl, or lower alkyl sub- H C CH stituted with loyer alkoxy,cyano, lower carboxylic a acide imido, or halogen; and

I H Cw K and R are the same or different and each repre- 2 sentshydrogen, lower alkyl, lower alkoxy or halogen.

wherein Q represents an acid anion. I References Cited {01112111 1?compound as defined in cla1m 1 having the UNITED STATES PATENTS3,243,298 3/1966 Libeer et a1 96-l05 8 OTHER REFERENCES Gi a; Q r Thieleet al., Annalen Der Chemie, vol. 347, pages x and to 126 (1906).Sparatore et al., Gazz. Chim. Ital. vol. 92, page 6H C on; (1962)- Il pJOHN D. RANDOLPH, Primary Examiner CIT 0 vs. C]. X.R.

wherein Q represents an acid anion. 855; 260-240], 240.9, 289, 309.2,326.11, 343.3, 465,

13. A compound having the following formula 576, 577, 578.

